Ceramic decalcomanias



Jan. l3, 1970 s. WEINGRAD 3,489,587

CERAMIC DECALCOMANIAS Filed Sept. 13, 1965 ATTORNEY United States Patent3,489,587 CERAMIC DECALCOMANIAS Saul Weingrad, Hillsdale, NJ., assignorto Commercial Decal, Inc., Mount Vernon, N.Y., a corporation of New YorkFiled Sept. 13, 1965, Ser. No. 486,953 Int. Cl. 341m 3/12 U.S. Cl.117-3.6 7 Claims ABSTRACT OF THE DISCLOSURE 'A vitreous decalcomania isformed from a contiguous design layer and film layer on a backingmaterial support. The design layer contains vitriliable oxide colorantsin a resinous vehicle and the' iilm layer contains oxide materials in aresinous vehicle. The resinous vehicles of each layer are ofsubstantially different polarity.

This invention relates to decalcomanias and more particularly to a noveldecalcomania for use in connection with ceramic ware.

In providing a decoration or insignia for ceramic ware, it hasheretofore been customary to use a water mount or slide olfdecalcomania. This type of decalcomania usually comprises a paperbacking, an imprinted design or insignia layer, and a so-called lacquerlayer. When this decalcomania is applied to the ware, the paper backingis removed by the' application of water. The provision of a lacquerlayer is essential in order that the integrity of the design bemaintained while removing the paper backing after the decalcomania hasbeen applied to the ware. The lacquer layer maintains the design orinsignia intact while transferring the decalcomania from the paperbacking to the ware itself. In addition the lacquer layer performs theadditional function of protecting the design layer during transport andstorage of the decalcomania and prevents deterioration or damage of thedesign or insignia.

After being initially formed to the desired shape, the ceramic ware iscovered with a glaze either before or after the application of thedecalcomania thereto. In the majority of instances, an underglazedecalcomania is provided in which the glaze is applied after thedecalcomania is placed on the ware. This method is widely used becausethe glaze thereafter acts as a protective coating over the decalcomaniaadding to the longevity and preventing deterioration of thedecalcomania. However, the glaze material is incompatible with theessential ingredients of the lacquer layer of the ceramic decalcomaniaand could not be applied thereover. Therefore it has heretofore beennecessary when providing underglaze decalcomanias to conduct at leasttwo firing operations in order to iirst remove the lacquer layer andthereafter to apply the glaze to the ware. This method was expensive andtime and labor consuming.

The lacquer layer comprises noxious materials and in those few instancesWhere the decalcomania is applied as an overglaze decalcomania, that is,over the glaze previously applied to the ware, these materials have adeleterious effect on certain colors of the pigment or design layer andon the decoration or insignia provided thereby when the ware is fired toharden on the decalcomania. Furthermore, the lacquer layer when red isodiferous, permeating the surrounding areas with undesirable odors anddetracting from the working conditions.

It has been suggested that a decalcomania be used whose paper backing isreleased by the presence of heat. This decalcomania, however, is quiteexpensive to produce and is not completely eicient. In addition, inapplying this decalcomania to the ware, it is necessary to provide anadditional coating in order to be able to secure the decalcomania forthe reason that the release media and the glaze are incompatible. Thisadditional step is also expensive and time and labor consuming.

There is a decalcomania whose paper backing is removable by the use of arelease media which softens in the presence of a chemical solvent. Thissolvent release type of decalcomania is seldom used in connection withmany types of ceramic ware for it is not at all adaptable for massapplication to ware. It is difficult, tedious and time consuming toapply, and in many instances two firing operations are required to applythe glaze and to harden on the decalcomania.

It is therefore an object of the present invention to provide a novelceramic decalcomania which eliminates the necessity for more than onefiring in applying both the underglaze decalcomania and the glaze itselfto the ware while nevertheless permitting the transfer of thedecalcomania to the ware without any damage to the design.

It is a further object of the present invention to provide a ceramicdecalcomania which is composed so as to eliminate the dispersion ofnoxious materials or odors during its application to the ware whilenevertheless being provided with a protective coating, preventing anydamage or deterioration of the design during transport or storage of thedecalcomania.

Still another object of the present invention is to provide a ceramicdecalcomania which requires no additional coating for the ware but whichis nevertheless positive and eicient in application.

Still a further object of the present invention is to provide a ceramicdecalcomania which is economical to produce while nevertheless beingcapable of rapid application to ware in volume.

`Other objects and advantages, as well as the features of the presentinvention, are described in greater detail in the followingspecification taken in conjunction with the drawings in which:

FIG. 1 is a diagrammatic cross-sectional view representing an embodimentof a ceramic decalcomania of the present invention; and

FIG. 2 is a diagrammatic cross-sectional view of another embodiment of aceramic decalcomania of the present invention.

Referring to the drawing of FIG. 1, the embodiment of the invention asillustrated therein comprises a ceramic decalcomania or transfer whichmay be produced by any suitable printing method, viz. lithography, silkscreen printing, rotogravure or the like. This decalcomania has abacking which is to be' released when the decalcomania is applied to theware. In the illustration this backing consists of a paper sheet 1. Thepaper sheet may be of the usual slide off type provided with a thinlayer of water soluble gum or adhesive or it may be the so-called duplexpaper. In either case it is removable when water is applied thereto. Alilm 2 is applied over the paper sheet, and imprinted over the lm is thedesign or insignia 3.

While the arrangement of the portions of the decalcomania and thefunctions of each layer may appear to be similar to those heretoforeused in the preparation of underglaze decalcomanias, nevertheless thenew and novel construction of the present invention comprises acombination of ingredients producing extremely beneficial results. Forexample, heretofore in applying underglaze decalcomanias after the paperwas removed or stripped off, it has been essential to tire the warebefore applying the glaze in order to burn off the previously usedlacquer layer and harden on the decalcomania. Thereafter it wasnecessary to again re the ware to apply the glaze, Thus two separate anddistinct expensive and time consuming firing operations were required.The use of the present invention, however, eliminates the necessity forthe dual firing operation by the provision of a novel l-m layer 2 anddesign layer 3 arrangement. This invention provides a decalcomania whoseiilm layer 2 is bonded suficiently to the design in order to protect thedesign during transport and storage. However, the structure is such thatthe iilm layer may be easily removed, manually or by air pressure or thelike from the design layer after the decalcomania is applied to the wareand witho-ut any initial ring operation. Thus the initial tiringoperation is eliminated with all of the consequent benefits attendantupon such elimination.

It has been discovered in accordance with the present invention thatthis new and extremely advantageous decalcomania is accomplishedaccording to the present invention by providing solids of high polaritycomprising the film when using solids of low polarity in the designpigment vehicle, or using solids of high polarity in the design pigmentvehicle when solids of low polarity comprise the film. For example, whencellulose esters are used as the solids in the film, cellulose ethersare utilized as the solids in the pigment vehicle. Furthermore, when theacrylics comprise the solids in the pigment vehicle, cellulose ethersmay be used to form the film cellulose esters or cellulose ethers may beutilized in the design pigment vehicle. With the use of thesecompositions, it is also possible to use a tremendous variety of colorsfor the design, and the brilliance of the colors themselves is enhanced.

In accordance with the present invention, various types and kinds ofsolvents may be used for the solids used in the lm and in the designpigment vehicle. The invention provides that where the design pigmentvehicle comprises solids which are soluble in aromatic or aliphatichydrocarbons, the solids contained in the lilm are to be soluble inesters and ketones. A decalcomania possessing the same advantages may beprovided according to the present invention where the solids of thedesign pigment vehicle are soluble in aromatic or aliphatic hydrocarbonsand the solids in the iilm are soluble in esters and ketones. Examplesof the typical formulations which may be utilized in providing thedecalco-mania of the present invention follow. Of course, the solventsare not limited to those specified in the examples as different onesWithin the same class may be used. Furthermore, the solids arespecilically defined merely for illustrative purposes and the amounts ofthe ingredients used are only illustrative.

' Where the lm comprises a cellulose ester as the solid, the designpigment vehicle contains a cellulose ether such as ethyl cellulose. Anexample of this composition is the following:

Film: Percent Cellulose acetate butyrate 20 Diacetone alcohol 8O Designpigment vehicle:

Ethyl cellulose (10 sec. visc.) 20 Plasticizer Butyl lactate 65Following the invention, cellulose ethers may be used in the hlmprovided that the solid of the design layer comprises acrylics asillustrated in the following example:

Film: Percent Ethyl cellulose sec. visc.) 15 Plasticizer 5 Solvesso 10050 Diacetone alcohol Design pigment vehicle:

Isobutyl methacrylie 20 Plasticizer l0 Solvesso 150 30 Butyl lactate 40Where vinyls are used in the lilm according to the present invention,cellulose esters may be used as the solid in the design pigment vehicle.An example of this is the following:

Film: Percent Vinyl chloride acetate copolymer 15 Plasticizer Diacetonealcohol 80 Design pigment vehicle:

Cellulose acetate butyrate 20 Plasticizer 15 Butyl lactate 65Furthermore, where vinyls are used as solids in the film, it is possibleto use cellulose ethers as, for example, ethyl cellulose in the designpigment vehicle. An example of this is as follows:

According to the present invention, where cellulose esters are used inthe film, butadiene styrene may be used as the solid in the designpigment vehicle. An example of this is as follows:

Film: Percent Cellulose acetate butyrate 20 Diacetone alcohol 80 Designpigment vehicle:

Butadiene styrene copolymer 20 Plaisticizer 15 Solvesso l5() 65 Anotherillustration of the use of solids of high and low polarity respectivelyin the iilm and the design pigment vehicle is the combination ofcellulose ethers, such as ethyl cellulose in the film and butadiene inthe design pigment vehicle. An example follows:

Film: Percent Ethyl cellulose (20 sec. visc.) 15 lPlasticizer 5 Solvesso100 50 Diacetone alcohol 30 Design pigment vehicle:

Butadiene styrene copolymer 20 Plasticizer 15 Solvesso 150 65 It hasbeen found that an effective strip-off film may be produced by utilizingpolystyrene in the design pigment vehicle and ethyl cellulose in thefilm. Exemplary of the formulae for these compositions is the following:

Film: Percent Ethyl cellulose (20 sec. visc.) l5 Plasticizer 5 Diacetonealcohol 80 Design pigment vehicle:

Polystyrene (low visc. grade) 30 Solvesso 150 70 Furthermore, the designpigment vehicle may comprise cellulose acetate butyrate in which thefilm would contain cellulose nitrate as disclosed in the following eX-ample:

Film: Percent Cellulose nitrate (5-6 sec. grade) 22 Plasticizer 4Diacetone alcohol 74 Design pigment vehicle:

Cellulose acetate butyrate (1/2 sec. grade) 25 Plasticizer Butyl lactate65 Film containing ethy=l cellulose may also be used according to thepresent invention when the design pigment vehicle is isobutylmethacrylic as follows:

It is also possible to use an oil modified alkyd in the design pigmentvehicle where ethyl cellulose comprises the solid in the film asfollows:

Film: Percent Ethyl cellulose Plasticizer 5 Diacetone alcohol 80 Designpigment vehicle:

Oil modified alkyd 50 Varsol 50 l The vehicle in this combinationcontains organometallic driers and would dry by solvent evaporation,polymerization and oxidation, thus, becoming insoluble in eithersubsequent coating operations or in solvents used to obtain adhesion ofthe film and pigment pattern to the ware.

It will be understood that all of the foregoing are detailed examples ofvarious compositions which may be used to provide a very effective stripoff film and are in no vway intended to be a limitation upon the broadconcept of the invention disclosed herein.

FIG. 2 illustrates a slide off type decalcomania in which the paperbacking is slid from under the design and film layer rather than removedIfrom over the design and film layer as is the case in FIG. l. Similarcompositions to those above specified may be used for it has beendiscovered according to the present invention that the desired resultsmay be accomplished when solids of low polarity are used in the filmtogether with solids of high polarity in the design pigment vehicle.Furthermore, when solids of high polarity are used in the film, solidsof low polarity are used in the design pigment vehicle. This arrangementwhich provides a film which Is readily strippable manually orautomatically from the design layer after application to the Ware andwithout firing, nevertheless also provides a sufficient degree ofadhesion between the design layer and the film to permit thedecalcomania to be shipped and stored without damage to the designlayer.

The preparation and application of the decalcomania to the ceramic wareare as follows: The slide off decalcornanias illustrated are printed ona standard sheet which has been coated with a water-soluble coating. Thefilm 2 is applied over the color film 3. The ware to be decorated shouldbe clean and dry. The decalcomania is then slid off the paper backingand applied to the ware. The decalcomania may then be squeegeed. Withinla relatively short period of time after the decalcomania istransferred, the film may be removed off the Ware by air pressure orstripped by hand. Removal by air pressure can be Iaccomplished by using.an air hose with any type nozzle. After the film is removed, the wareis permitted to dry and the glazing process may begin. There is nofiring necessary until the firing required to apply the glaze.

It is to be understood that while the invention has been described ingreat detail, and with many examples to illustrate a portion of thescope thereof, nevertheless these illustrations and the detaileddescription are not to be construed as limiting the scope `or spirit ofthe invention as it is defined in the appended claims.

What is claimed is:

1. A vitreous decalcomania comprising a backing sheet adapted to beremoved prior to the application of the decalcomania to ceramic ware,

a printed design layer on said backing sheet consisting of ceramic oxidecolorants in a resinous vehicle of one polarity,

a film layer consisting of a resinous vehicle of a polarity differentfrom that of the design layer,

said design and film layers being disposed immediately adjacent to andin surface contact with each other, the resinous vehicle in one of saidlayers being of a high polarity and the resinous vehicle in the othersaid layer being of a low polarity,

said film layer adherent to the design layer but readily removable fromthe said design layer prior to firing the design layer directly on theware,

whereby said design layer only is firmly adhered to the ware in onefiring operation together with an overglaze.

2. A vitreous decalcomania in accordance with claim 1 wherein said filmlayer ycomprises ethyl cellulose as the resinous vehicle and said designlayer comprises a polystyrene resin as the resinous vehicle.

3. A vitreous decalcomania in accordance with claim 2 wherein said lmlayer comprises cellulose acetate butyrate as th-e resinous vehicle andsaid design layer comprises butadiene-styrene copolymer.

4. A vitreous decalcomania in accordance with claim 1 wherein said lmlayer is formed with ethyl cellulose as the resinous vehicle and saiddesign layer is formed with isobutyl methacryate as the resinousvehicle.

5. A vitreous decalcomania in accordance with claim 1 wherein said lmlayer is formed with vinyl chloride acetate copolymer as the resinousvehicle and said design layer is formed with cellulose acetate butyrateas the resinous vehicle.

6. A vitreous decalcornania in accordance with claim 1 wherein said filmlayer is formed with vinyl chloride acetate copolymer as the resinousvehicle and said design layer is formed with ethyl cellulose as theresinous vehicle.

7. The vitreous decalcomania according to claim 1 wherein the said filmlayer is formed of cellulose acetate butyrate as the resinous vehicleand said design layer is formed with ethyl cellulose as the resinousvehicle.

References Cited UNITED STATES PATENTS 10/1930 Laws 1l7--3.6 l/ 1933Mitchell et al 1l7-3.6 3/1938 McNutt 156-89 2/1953 Rathke 1l7-3 .62/1956 Karne 156-140 5/1956 Matthes 156--140 1/1961 Porth 156-89 11/1961Akkeron 156-8 1/1962 Gobel 117-3.6

FOREIGN PATENTS 12/ 1959 Canada.

MURRAY KATZ, Primary Examiner U.S. C1. X.R.

